Sterically hindered cyclopentadienyl and phospholyl ligands in dysprosium chemistry

Add time:08/09/2019    Source:sciencedirect.com

Three new unsolvated organometallic complexes of dysprosium(III) with very sterically hindered π-ligands have been synthesized and structurally characterised: the monomeric bis[η5-(1,2,4-tris-trimethylsilylcyclopentadienyl)]iododysprosium (1b), bis[η5-(1,4-bis-t-butyl-2,3-dimethylphospholyl)]iododysprosium, (1c) and the dimeric tetrakis[η5-(1,4-bis-t-butyl-2,3-dimethylphospholyl)]bis(μ-iodo)di-dysprosium (1d). The relative steric bulk of the π-ligands have been assessed by comparison of the structural data of 1b–d with that of the previously described bis[η5-(1,2,4-tris-t-butylcyclopentadienyl)]iododysprosium (1a). Contrary to 1a, reduction attempts on 1b–d were unsuccessful. The reaction of the dysprosium(II) complex bis[η5-(1,2,4-tris-t-butylcyclopentadienyl)]dysprosium(μ-bromo)-potassium[18]crown-6 (3) with fluorenone resulted in its monoelectronic reduction and coordination of the resulting ketyl to dysprosium(III): isolation of potassium[18]crown-6 bis[η5-(1,2,4-tris-t-butylcyclo-pentadienyl)](fluorenone ketyl)bromodysprosate (4) that was structurally characterised.

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